Diamide textile lubricants



Patented Aug. 12, 1941 Q 2,425,392

UNITED STATES, PATENT" ornca DIAMIDE TEXTILE LUBRICANTS Edwin A. Robinson, Chatham, and Maurice J. -Kelley, Newark, N. J., assigiiors'to Nopco Chemical Company, Harrison, N. 5., a corporation of New Jersey No Drawing. Application June 23, 1943,

1 Serial No. 491,969

19 Claims. (fit. 260-4045) .2 This invention relates to textile lubricants and We have now found that diamides having the softeners, and more particularly to textile lubrigeneral formula: cants and softeners comprising mixed fatty di- (1) 0 amides. This application is a continuation-ini part of the copending application of Robinson 5 wherein. and Kelley Serial No. 274,808, filed May 20, 1939, now Patent No. 2,345,632.

It has been proposed to use higher fatty Rii Such as acid amide oleic acid represents a fatty acyl radicle containing from 8 methyl amide and oleic acid ethylene diamide, 10 to 22 carbon atoms; as softeners and lubricants for textile materials. 0 Such amides are ordinarily prepared by reacting a fatty acid or fatty ester with a mono or polyamine. The reaction of monoamines with higher represents a fatty acyl radicle containing from fatty acids or fatty esters yields products which 2 to 5 carbon atoms: R: in each occurrence, and ar n t re d y spe si e in wat r and en e independently of its other occurrence, represents these products cannot be advantageously applied a. hydrogen atom or an alkyl radiclc; and X repto textile mat ial. It h n p posed, thereresents an aliphatic linking chain which may be fore, to react polyamines with higher fatty acids branched or interrupted by ether or keto groups, or fatty esters to produce amides having free may be applied to textile materials so as to imamino roups cap e of r in with weakacids part thereto excellent softness, drape and pliaso as to solubilize the products and render them bility. These diamides are also highly useful as readily dispersible or soluble in water. However, synthetic waxes and as ingredients in cosmetics, the monoamides formed from such polyamines defoaming compositions and the like. The diby reaction thereof with higher fatty acidsor amides of this invention are readily prepared by fatty esters cause yellowing of textile material reacting a diamine such as ethylene diamine, upon application thereto and hence are highly N-methyl ethylene diamine, 1,6 diamino hexane,

unsuitable for use as textile lubricants and softetc., with a fatty acid. containing from 8 to 22 eners. On the other hand, polyamides formed by carbon atoms, or an ester or acid halide thereof, 5 the reaction of higher fatty acids or fatty esters and .with a short-chain fatty acid containing with polyamines are much less desirable as softfrom 2 to 5 atoms, or an ester, anhydride or acid eners and lubricants than the corresponding halide thereof. Th foregoing reactions may be monoamides because of their relatively poor softcarried out in either order or simultaneously, 1. e., ening and lubricating pr perties. the higher fatty acid materia1 may be condensed It has also been proposed to prepare textile 5 with the diamine to form a monoamide after lubricants and softeners by reacting unsymmetriwhich the lower fatty acid material is condensed cal dialkyl ethylene diamines with higher fatty with the monoamide; or the lower fatty acid may acids such as oleic acid. Such unsymmetrical b condensed with the diamine and the resultant dialkyl amines are, however, relatively expensive monoamide condensed with the higher fatty acid and difiicult to obtain andhence, while amides 4 material; or all the reagents may simultaneously thereof have been used to some extent as textile be condensed. The first method will usually be lubricants and softeners, there is a great demand preferred for manipulative reasons. The resultin the textile industry for cheaper products ant' diamides, although they are less readily diswhich may be used in place of these amides. persible than the acid-solubilizible secondary- It is an object of this invention to provide in amino-group-containing polyamides of the parexpensive and highly effective textile lubricants ent application above referred to, may, neverand softeners. theless, be dispersed in water, by th use of suit- It is a further object of this invention to proable emulsifiers, if necessary, and may be applied vide a process for the preparation of textile lubrito textile in that form. Moreover, the diamides cents and softeners from polyamines. of this invention may likewise be applied to textiles in solvent solution. Textiles so treated have admirabl softness but are not adversely affected as to color. The products are also useful as ingredients in synthetic wax compositions. defoaming compositions, emulsifying agents for waterin-oil emulsions, and the like.

Diamlnes which may be used as starting materials in the process of this invention are any aliphatic compounds containing two amino groups (primary or secondary) joined by an aliphatic group, which may optionally be interrupted by ether groups, having the formula:

R; R: eight-n under the notation of formula (1) supra. Such diamines are exemplified in ethylene diamine, N-methyl ethylene diamine, N,N' diethyl ethylene diamine, symmetrical diamino ethyl ether, 1,6 diamino hexane, and the like.

The long chain fatty acid compound reacted with the polyamine in accordance with our invention may be any of the fatty acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, or the esters or acid halides thereof; the following higher fatty acids may be mentioned by way of examples: caprylic acid, nonylic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, ricinoleic acid, mixtures of these acids, etc. In place of the higher fatty acids, derivatives thereof such as glycerides and other esters may be employed. Actually, we prefer to use glycerides of the fatty acids since products are obtained having superior softening properties to those resulting from the reaction of the polyamines with the free fatty acids. Products particularly suitable as textile lubricants and softeners are obtained by employing coconut oil to react with the polyamines in accordance with our invention, since these products are more readily dispersible in water and possess excellent lubricant and softening properties. As examples of other glycerides that may be employed in place of the long chain fatty acids, there may be mentioned teaseed oil, castor oil, hydrogenated castor oil, etc.

The short chain acids employed in accordance with our invention contain from 2 to carbon atoms; thus, for example, acetic acid, glycollic acid, lactic acid, propionic acid, butyric acid and valeric acid maybe employed; derivatives thereof such as esters, acid halides and anhydrides may be employed in accordance with procedures well known to the art. We prefer to use acetic acid or acetic anhydride in the preparation of our novel products because of their ready availability and. the excellent softening properties of the amides prepared from these compounds.

. In carrying out the reaction in accordance with our preferred method, approximately equimolecular quantities of a polyamine and a fatty acid containing from 8 to 22 carbon atoms are mixed; if a glyceride of a fatty acid is employed, e. g., coconut oil, approximately V3 mol of the glyceride per mol of polyarnine is used. The compounds are then permitted to react at a temperature sufliciently high to cause the formation of the monoamide; this temperature may vary from about 120 C. to about 200 C. butpreferably is between about 150 C. and about 170 C. The time of this reaction may vary widely depending somewhat upon the particular reactants and somewhat upon the temperature; generally, 8 hours or more are required. The pressure under which the reaction is carried out is preferably 4 I atmospheric; however, pressures above or below atmospheric may be employed. The product of the reaction is then mixed with a suitable quantity of a short chain fatty acid containing from 2 to 5 carbon atoms; as above mentioned, anhydrides, esters or acid halides of these acids may also be employed. The conditions under which this reaction is carried out may vary widely, but we havefou'nd that the constituents may be reacted at atmospheric pressure and at a temperature of about 135 C. for about 3 to 5 hours, the mixture then raised to between about'150" C. and about 170 C. and the reaction continued for about 5 to about 8 additional hours with excellent results. However, it is to be understood that these conditions may be varied somewhat. without affecting the course of the reaction, e. g., pressures above or below atmospheric may be used, the temperatures may vary widely so long as they are sufficiently high to effect acylation, and the time of reaction may differ from the time above set forth.

The products of this invention may be liquids or solids, but generally they are solids. The products are in general insoluble in water; however, they may readily be dispersed in Water by the use of suitable emulsifiers. Our novel products may be marketed as such or in the form of an aqueous dispersion or paste, or in the form of a solvent solution thereof. They may be applied to textile materials by any of the well known methods, e. g., in the form of an aqueous dispersion. or solvent solution thereof, and in every case impart excellent softness, drape, flexibility and handle to the textile material. The products are further adapted for use as synthetic waxes or ingredients in synthetic wax. Further, the products may be used in cosmetics, defoaming compositions, emulsifying agents for waterin-oil emulsions, as plasticizers and the like.

The following examples are illustrative of our invention, all parts given being by weight:

Example I Coconut oil 230 parts mol) Ethylene diamine parts (1 mol) Acetic anhydrlde 50 parts (/2 mol) The ethylene diamine and coconut oil were mixed in an open kettle and agitated at temperatures between 150 and 170 C. for 8 hours. The acetic anhydride was then added to the reaction product and the mixture agitated at a temperature of 135 C. for 3 hours, after which the temperature was raised and the reaction continued at temperatures between 150 and 170 C. for an additional 5 hours. A solid product relatively insoluble in water was thereby obtained which was suitable 'as a textile dressing or as a synthetic wax.

Example II Hydrogenated tallow (iodine value 10) 82 parts /3 mol) Ethylene diamine 18 parts (1 mol) Glycollic acid (70% aqueous) 30 parts (1 mol) aczasee ture which was admirably adapted as a hard wax substitute.

Example III Oleic acid 282 parts (1 mol) Ethylene diamine 166 parts (1 mol) Acetic anhydride 51 parts (/2 mol) Example IV Stearic acid 284 parts (1 mol) Symmetrical diethyl ethylene diamine 156 parts (1 mol) Lactic acid (85% aqueous) 106 parts (1 mol) The stearic acid and diethyl ethylene diamine were agitated together at temperatures between 150 C. and 170 C. for 12 hours. Thereafter the mixture was cooled down to 70 C., the lactic acid stirred in and the temperature again raised to 150 C. for 3 hours. The resultant product was a solid at room temperature.

From the foregoing general discussion and specific examples, it will be apparent that this invention provides novel diamide products suitable for a wide range of uses, notably as textile lubricants, synthetic waxes, ingredients in defoaming agents, emulsifiers for water-in-oil emulsions, and the like. The products may be prepared from the readily and cheaply procurable higher fats and fatty acids and lower fatt acids and aliphatic diamines and are synthesized bya process which may be carried out by relatively unskilled operatives in conventional equipment.

We therefore claim:

l. Diamides having the general formula:

wherein R1CO- represents an aliphatic acyl radicle containing from 8 to 22 carbon atoms; -0CR2 represents a fatty acyl radicle containing from 2 to 5 carbon atoms; R: in each occurrence, and independently of its other occurrence, represents a substituent chosen from the group consisting of hydrogen atoms and alkyl radicles; and -X-- represents an aliphatic linking chain selected from the group consisting of bivalent hydrocarbon chains and bivalent hydrocarbon chains interrupted by an ether linkage.

2. Diamides according to the general formula of claim 1, wherein X- more particularly represents an aliphatic hydrocarbon chain.

3. Diamides according to claim 1, -X- more particularly represents the group 'CH2--CH2-.

4. Diamides according to'the formula of claim 1, wherein R1--CO- more particularly represents the fatty acyl radicles contained in a fatty glyceride oil.

5. Diamides according to the formula of claim 1, wherein R1-CO more particularly represents the fatty acyl radicles contained in coconut oil.

6. Diamides according to the formula of claim wherein 1, wherein more particularly represents the fatty acyl radicles contained in hydrogenated tallow.

7. Diamides according to claim 1, having the more particular formula: 11 1|! al-c O-N-X-N-0 c-cn= under the notation of claim 1.

8. Diamides according to claim 1, having the more particular formula:

Ilia 1?: 111-0 0-NXN0 o-cm-on under the notation of claim 1.

9. Diamides having the general formula:

llh 1F: m-c o-NcH,cH,-N-0 c-R,

' wherein R1CO-- represents the fatty acyl radicles contained in a glyceride oil; -0C-Rc represents an aliphatic acyl radicle containing from 2 to 5 carbon atoms and Rs in each occurrence, and independently cfits other occurrence, represents a substituent chosen from the group consisting of hydrogen and alkyl radicles.

10. Diamides according to claim 9, wherein R1C-O- more particularly represents the fatty acyl radicles contained in coconut oil.

11. Diamides according to claim 9, wherein R1--C-O more particularly represents the fatty acyl radicles contained in hydrogenated tallow.

12. A diamide having the general formula:

wherein R1--CO represents the fatty acyl radicles contained in a glyceride oil.

13. A diamide having the general formula:

HHHH

wherein R1 C0 represents the fatty acyl radicles contained in a glyceride oil.-

14. A diamide having the general formula:

radicles contained in coconut oil.

15. Process which comprises condensing by heating at a temperature between about 120 C.

and about 200 C. a diamine having the formula:

II Ilia H-N-X-NH bon chains interrupted by an ether linkage with approximately a fatty acid molecular equivalent of a. substance chosen from the group consisting of higher fatty acids containing from 8 to 22 carbon atoms and the esters and acid halides thereof; and with approximately an acid molecular equivalent of a substance'chosen from the group consisting of lower aliphatic acids contain- 7 ing from 2 to 5 carbon atoms and the esters, anhydrides, and acid halides thereof.

16. Process according to claim 15, wherein the substance chosen from the group consisting of higher fatty acids and the esters and halides thereof is a fatty glyceride oil.

17. Process according to claim 15, wherein the substance chosen from the group consisting of higher fatty acids and the esters and halides thereof is coconut oil.

18. Process according to claim 15, wherein the substance chosen from the group consisting of higher fatty acids and the esters and halides thereof is hydrogenated tallow.

19. Process according to claim 15, wherein the condensations between the several ingredients are eflected in stages, the diamine being first condensed with the substance chosen from the group consisting of higher fatty acids and esters and acid halides thereof to form a monoamide, and

8 in which the resulting monoamide is then further condensed with the substance chosen from the group consisting of lower fatty acids and the esters and acid halides thereof.

EDWIN A. ROBINSON.

MAURICE J. KELLEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,090,595 Jacobson Aug. 17, 1937 2,139,679 Hardy Dec. 13, 1938 2,279,497 Sallmann et al Apr. 14, 1942 2,321,186 Christmann June 8, 1943 2,243,329 DeGroote May 27, 1941 2,243,980 Rheiner et a1. June 3, 1941 2,345,632 Robinson et a1. Apr. 4, 1944 

